Pentaalkylstiboranes. 1. Synthesis of Homobenzylic Alcohols, Homoallylic Alcohols, Ethyl 5-Aryl-5-hydroxypent-2-enoates, and β-Hydroxypropionic Acid Derivatives via Pentaalkylstiboranes

Article abstract of DOI:10.1021/jo00004a010

Although pentaalkylstiboranes have long been known, their applications in organic synthesis have not been exploited.It has been found that quaternary stibonium salts (n-Bu3SbCH2E)⁺X^- (E = Ph, CH=CH2, CH=CHCO2Et, CO2Et, CN; X = Br, I, BPh4) on treatment with RLi (R = n-Bu, t-Bu, Ph) afford pentaalkylstiboranes, n-Bu3Sb(R)CH2E, which react with aromatic aldehydes to give, after subsequent hydrolysis, homobenzylic alcohols, homoallylic alcohols, ethyl 5-aryl-5-hydroxypent-2-enoates, and β-aryl-β-hydroxypropionitriles, respectively, in good to excellent yields.The reaction is chemoselective for aldehydes.